Insecticide



Patented Jan. 10, 1928.

UNITED STATES ROLAND P. SOULE,

PATENT oFFlcs.

OF NEW YORK, N. Y., 'AS SIGNOB TO COMBUSTION UTILITIES COB;

PORATION, 01 NEW YORK, N. Y., A OONPORATION 01' MAINE.

msncrrcmn.

' no Drawing.

This invention relates toinsecticides, and more particularly to a new and useful article of manufacture, which possesses valuable insecticidal properties.

6 Pyridine, which is the simplest nitro en base of ordinary coke-oven tar, is known to be poisonous to fly larvae, maggots, and other pests, but it is expensive and too limited in its effectiveness for general commercial ap- 10 plication. Nicotine, which-contains a pyrrolidine group, as well as a pyridine nucleus,

trogen bases of coal tar have had no imporp tant industrial application as insecticides,-

and the use of nicotine and compounds derived therefrom is restricted by their expense.

The primary object of the present invention is the production of a nitrogenous insecticide that is both effective and relatively inexpensive.

.The composition comprising the subject matter of the present invention may be described as consisting essentially of a mixture of organic heterocyclic nitrogen compounds soluble in dilute mineral acid (e. g. 20% sul- -furic acid) and/or of the hydrochloride or sulphate salts-of said compounds; these compounds being the hydrogenated and alkylated derivatives of pyridine, quinoline, acridine, and homologous polycyclic nitrogen bases which are found in coke-oven tar. These products difl'er from nicotine by the absence of a pyrrolidine group, and they dif: for from pyridine and the related nitrogen 40 bases in coke-oyen tar in their higher content of hydrogen and usually also in their v greater number of alkyl' side-chains. This difference in constitution is indicated by the fact that the nitrogen compounds forming the subject of the present invention have a higher molecular weight, lower dens1ty and lower refractive index than coke-oven nitrogen bases of similar boiling range. It is believed, moreover, that this higher content of cidw.

Application filed June 83, 1924. Serial 10.721389.

hydrogen and alkyl groups is the chief reason for their increased effectiveness and broadened scope of application as insecti- This mixture of orgiinic heteroc clic nitrogen compounds can e repared rom the liquid products of disti ation of coal or other bituminous material, provided that the conditions of the distillation are sufliciently mild to preserve these liquid products in their primary state, e. g., substantially unaltered in composition and largely protected from secondary decomposition into compounds of the aromatic series. In the patent to HenryL. Doherty No.,1,426,159, granted August 15, 1922, and in the British atent of Henry '0. Loebell, 216,388- of May 23, 1923, Manufacture of 'fuel gas, two gas making processes are described, by either of which fuel is distilled under such mild conditions as to produce substantially primary tar. In theseprocesses the fuel is passed downwardly through a. shaft furnace at a gradual rate and during its passage through the furnaceit is heated and carbonized solely by sensible heat supplied by a rising current of hot gases. By passing this gas current in a. direction opposed to that in which the fuel is advancing the fuel isheated gradually and the gas is correspondingly cooled through the transfer of its heat. This method of operation results in exceedingly mild conditions of distillation and carbonization, since the volatile products distilled from the coal are mixed with and carried off by the current of heating gas rising through the upper and cooler portions of the charge. Thus the tar vapors are not exposed to temperatures much above those atwhich they are first liberated, and therefore are almost completely preserved .in their primary composition.

This primary tar is clearly distinguishable both in chemical and physical properties. from ordinary tars produced at the high temperatures of the gas-works or coke-oven. For example, the nitrogen compounds present in coke-oven'tar consist almost entirely of tertiary bases of the pyridine-quinoline- I acridine series. They may be regarded as compounds derived from the aromatic hydrocarbons by the replacement of a carbon atom bya nitrogen atom, and 'just as naphthalene preponderates among the hydrocarbons of coke-oven tar, so does quinoline, or the tertiary nitrogen base derived from naphthalene, preponderate among the nitrogen bases of coke-oven tar. The nitrogen bases of a primary tar such as described above, on the other hand, may be regarded as compounds derived from the hydroaromatic or cyclic unsaturated non-benzenoid hydrocarbons. No

tiary and secondary'bases.

I acid solution by treatment with caustic al-,

This mixture of primary nitrogen bases and/or of the mineral acid salts of such bases possessesvaluable insecticidal properties, and in. addition can beproduced at relatively small cost. The primary tar is distilled to a soft pitch and'the distillate freed of tar acids by extraction with weak alkali;

If the tar hasbeen produced from ordinary bituminous coal, the residual oil may contain' two to three percent of nitrogen bases, and is then treated with twenty percent sulfuric acid or with other dilute mineral acid. The nitrogen bases or convenient fractions thereofwhich are liberated from the kali comprise the mixture which is the subject of the present invention. Because of the large proportion of valuable and useful products which can be obtained from the primary liquid distillates of coal or other bituminous material, the manufacturing costvof this insecticidal agent is proportionately The-following brief description is offered as a specific example of the procedure to be followed in the preparation of a water soluble insecticide of the character'comprising the subject of the present invention :-A primary tar obtained by the mild carbonization of Elkhorn coal in accordance with the process described in the aforementioned Loebell British Patent.216,388, May 23, 1923, is dis tilled to an end point at which a pitch residue having a 150 F. melting point is obtained. The distillate formed comprises by volume about 50% of the original primary tar and it contains by volume upwards of 25% of tar acids. This distillate is ex- I tracted with a 10% sodium hydroxide solution, the volume of hydroxide used being sutficient to effect the complete removal of the tar acid content of the distillate. The tar acid free distillateis then extracted with dissolved in the oil.

neutralizing the extract with caustic alkali.

To every 20 grams of the nitrogen bases thus liberated there is.

added 6.8 grames of rosin and the mixture is heated with stirring until the rosin has To this mixture 4 cc. of sodium hydroxide solution is added, of such concentration that there are 200 grams of sodium hydroxide per liter of solution, and theheat-ing and stirring is continued until foamingcommences. The mixture is then allowed to cool, and diluted with water to give stable emulsions of any desired concentration of nitrogen bases.

These nitrogen bases have been found of value either by themselves or in admixture with tar-acids or other primary tar compounds, not only in making up insecticidal and disinfectant oils, but also as flotation oils and for other purposes. It will be apparent that they can be preparedfrom any sort of coal or bituminous material by any distillation process wherein the conditions are sufiicient y mild to preserve the primary nitrogen bases in a substantially condition. y

The subject matter of the present invention having been thus described, what is claimed as new is:

1. An insecticide containing hydrogenated and alkylated derivatives of pyridine, quinoline, acridine and homologous polycyclic nitrogen bases in admixture with a mineral acid salt of the same.

2. An insecticide containing a mixture of the organic hetero-cyclic nitrogen compounds naturally occurring in the tar acid free distillate of'a primary tar of the class described.

3. An insecticide containing a mixture 'of the hydrogenated derivatives of pyridine, quinoline, acridine and homologous poly-cyundecomposed acid extract are clic nitrogen bases naturally occurring-1n the v tar acid free distillate of a primary tar of genated and alkylated derivatives or pyridine, quinoline, acridine and homologous poly-cyclic nitrogen bases.

6. An insecticide containing hydrogenated and alkylated derivatives of quinoline, acridine and homologous poly-cyclic nitrogen bases.

7. An insecticide containing the salts produced by reacting a mineral acid with the alkylated derivatives of pyridine, quinoline, oline in admixture with other nitrogen base 1 'acridine and homologous poly-cyclic nitroderivatives of cyclic unsaturated non-bengen bases. zenoid hydrocarbons.

,8; An insecticide containing salts pro- 10. An insecticide containingdihydro-iso- 5 duced by reacting a mineral acid with the quinoline in admixture with other nitrogen hydrogenated derivatives of pyridine, quinobase derivatives of cyclic unsaturated non- 15 line, acridine and homologous poly-cyclic nibenzenoid hydrocarbons. trogen bases. In testimony whereof I afiix my signature.

9. An insecticide containing dihydroquin- ROLAND P. SOULE. 

